JP2013103990A - Resin composition, and film, anti-fogging film, antifungal film and coating agent using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition useful for obtaining a film and a coating agent which are excellent in antifogging performance and excellent in antibacterial adhesion.
A resin composition comprising an acetoacetyl group-containing polyvinyl alcohol resin (A), a glyoxylate (B), and a fluorine-containing nonionic surfactant (C).
[Selection figure] None

Description

  The present invention relates to a resin composition and a film using the same, and more particularly to obtain a film excellent in antifogging property and antibacterial adhesion property (sometimes referred to as antibacterial adhesion property) and a coating agent. The present invention relates to a resin composition useful for.

  Cloudiness due to condensation on the glass surface hinders visibility. As countermeasures, methods such as keeping the glass warm with a heating wire or superhydrophilic treatment on the surface of the glass are taken, but in any case, an increase in cost is inevitable. Therefore, as a simple means, a method of attaching an antifogging film to the glass surface has been proposed and put into practical use.

For the antifogging layer of such an antifogging film, a polymer material having excellent hydrophilicity and transparency is used, and a typical example is a polyvinyl alcohol resin (hereinafter abbreviated as PVA resin). However, since the PVA resin is a water-soluble polymer, it has inherently poor water resistance, and has a problem that the physical properties change greatly upon moisture absorption or water wetting. There is a need for improvements.
In order to solve such a problem, a method of crosslinking a PVA resin is effective. For example, a modified PVA resin having a reactive acetoacetyl group in the side chain and an antifogging layer containing a crosslinking agent are included. An antifogging sheet has been proposed (see, for example, Patent Document 1).

JP 2000-000935 A

  However, the antifogging sheet described in Patent Document 1 is required to be further improved in terms of antifogging performance required at the time of use in recent severe environments. Sheets are often used in a constantly humid environment such as bathrooms, hot springs, and swimming pools. Under such circumstances, once bacteria adhere to the sheets, they adhere to the sheets. There was a risk that various fungi would propagate and cause infections.

  Therefore, the present invention aims to provide a resin composition useful for obtaining a film or a coating agent that is excellent in antifogging performance and excellent in antibacterial adhesion under such a background. is there.

However, the present inventors have made extensive studies in view of such circumstances, and as a result, the resin composition for an antifogging film comprising a modified PVA resin containing an acetoacetyl group and a crosslinking agent, which has been conventionally used, contains fluorine. It has been found that the addition of a nonionic surfactant not only improves the anti-fogging performance of the resulting film, but also improves the anti-bacterial adherence, leading to the completion of the present invention.
In the present invention, by adding a fluorine-containing nonionic surfactant, the water contact angle on the surface of the film is reduced, so that it is presumed that the antibacterial adhesion is also effective.

That is, the gist of the present invention is a resin composition comprising an acetoacetyl group-containing polyvinyl alcohol resin (A), a glyoxylate (B), and a fluorine-containing nonionic surfactant (C). It is about things.
Furthermore, this invention relates to the film and coating agent which use the said resin composition.

  A film using the resin composition of the present invention and a coating film coated with the resin composition of the present invention as a coating agent have excellent antifogging performance and excellent antibacterial adhesion. .

  The present invention will be described in detail below, but these show examples of desirable embodiments.

First, an acetoacetyl group-containing polyvinyl alcohol resin (A) (hereinafter sometimes referred to as “AA-modified PVA resin (A)”), glyoxylate (B), and fluorine-containing nonionic surfactant The resin composition containing (C) will be described.

[Acetacetyl group-containing polyvinyl alcohol resin (A)]
The AA-PVA-based resin (A) used in the present invention is a PVA-based resin having an acetoacetyl group in the side chain.

  The method for producing the AA-PVA-based resin (A) is not particularly limited. For example, the PVA-based resin is reacted with diketene, and the PVA-based resin is reacted with acetoacetate for transesterification. Method, a method of saponifying a copolymer of vinyl acetate and vinyl acetoacetate, and the like. However, since the production process is simple and a good quality AA-PVA-based resin (A) is obtained, the PVA-based It is preferable to produce the resin by a method of reacting diketene. Hereinafter, this method will be described.

  As the PVA resin used as a raw material, a saponified product of a vinyl ester monomer polymer or a derivative thereof is generally used. Examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, and valeric acid. Examples include vinyl, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl versatate, and vinyl acetate is preferably used from the viewpoint of economy.

Further, a saponified product of a copolymer of a vinyl ester monomer and a monomer copolymerizable with the vinyl ester monomer can be used. Examples of the copolymer monomer include ethylene, propylene, isobutylene, α- Olefins such as octene, α-dodecene, α-octadecene, hydroxy such as 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 3,4-dihydroxy-1-butene Derivatives such as group-containing α-olefins and acylates thereof, unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, undecylenic acid, salts, monoesters, or dialkyl esters thereof , Nitriles such as acrylonitrile and methacrylonitrile, diacetone acrylate Amides such as amide, acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid or salts thereof, alkyl vinyl ethers, dimethylallyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinyl Vinyl compounds such as ethylene carbonate, 2,2-dialkyl-4-vinyl-1,3-dioxolane, glycerol monoallyl ether, substituted vinyl acetates such as isopropenyl acetate and 1-methoxyvinyl acetate, vinylidene chloride, 1, 4-diacetoxy-2-butene, 1,4-dihydroxy-2-butene, vinylene carbonate and the like can be mentioned.
The introduction amount of the copolymerization monomer varies depending on the type of the monomer and cannot be generally specified. However, it is usually 10 mol% or less, preferably 5 mol% or less of all structural units. If the amount introduced is too large, the water solubility tends to be impaired, or the compatibility with the crosslinking agent tends to decrease.

  In addition, the polymerization temperature when polymerizing vinyl ester monomers or copolymerizing vinyl ester monomers and other monomers is adjusted, and the amount of heterogeneous bonds produced mainly with respect to the 1,3-bonds produced is increased or decreased. It is possible to use those in which the 1,2-diol bond in the main chain is about 1.0 to 3.5 mol%.

  The introduction of acetoacetyl groups by the reaction of PVA resin obtained by saponifying the polymer and copolymer of the above vinyl ester monomer and diketene involves direct reaction of PVA resin with gaseous or liquid diketene. Alternatively, after adsorbing and occluding an organic acid in a PVA resin in advance, a gaseous or liquid diketene is sprayed and reacted in an inert gas atmosphere, or a mixture of an organic acid and a liquid diketene is applied to the PVA resin. Methods such as spraying and reacting are used.

  As a reaction apparatus for carrying out the above reaction, an apparatus that can be heated and has a stirrer is sufficient. For example, a kneader, a Henschel mixer, a ribbon blender, other various blenders, and a stirring and drying apparatus can be used.

  The average polymerization degree of the AA-PVA-based resin (A) thus obtained is usually from 300 to 5,000, preferably from 500 to 2,000, particularly preferably from 1,000 to 1,500. If the average degree of polymerization is too small, the strength of the antifogging layer tends to be insufficient or sufficient water resistance cannot be obtained. Conversely, if it is too large, the viscosity of the coating solution for forming the antifogging layer Tends to be too high, and workability tends to decrease.

  The degree of saponification of the AA-PVA-based resin (A) used in the present invention is usually 60 mol% or more, preferably 80 mol% or more, particularly preferably 90 mol% or more, more preferably 98 mol%. That's it. If the degree of saponification is too low, the antifogging property tends to be insufficient because the affinity between the obtained antifogging layer and water decreases. The average degree of polymerization and the degree of saponification are measured according to JIS K6726.

  Further, the content ratio of the acetoacetyl group in the AA-PVA-based resin (A) (hereinafter abbreviated as AA degree) is usually 0.1 to 20 mol%, preferably 1 to 15 mol%, especially Preferably it is 3-10 mol%. If the content is too small, the water resistance of the anti-fogging layer tends to be insufficient. Conversely, if the content is too large, the affinity of the anti-fogging layer and water decreases, and the anti-fogging property tends to be insufficient. There is.

  In the present invention, it is preferable that all of the PVA resins contained in the resin composition are AA-PVA resins (A), but PVA resins other than AA-PVA resins (A) are used in combination. The content ratio is usually 20% by weight or less, preferably 10% by weight or less, based on the total amount of the PVA resin.

  Examples of PVA-based resins other than the AA-modified PVA-based resin (A) include unmodified PVA and various modified PVA-based resins such as a vinyl ester monomer and a monomer copolymerizable with the vinyl ester monomer. A saponified product of the above copolymer may be used. Examples of such monomers include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, 3-buten-1-ol, Hydroxyl group-containing α-olefins such as 4-penten-1-ol, 5-hexen-1-ol, and 3,4-dihydroxy-1-butene and derivatives such as acylated products thereof, acrylic acid, methacrylic acid, crotonic acid , Unsaturated acids such as maleic acid, maleic anhydride, itaconic acid, undecylenic acid, salts thereof, monoesters, Or nitriles such as dialkyl esters, acrylonitrile and methacrylonitrile, amides such as diacetone acrylamide, acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid or salts thereof, alkyl vinyl ether , Dimethylallyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinyl ethylene carbonate, 2,2-dialkyl-4-vinyl-1,3-dioxolane, vinyl compounds such as glycerol monoallyl ether, isopropenyl acetate, 1- Examples thereof include substituted vinyl acetates such as methoxyvinyl acetate, vinylidene chloride, 1,4-diacetoxy-2-butene, 1,4-dihydroxy-2-butene, vinylene carbonate and the like.

  In addition, the AA-PVA-based resin (A) of the present invention includes an alkali metal acetate such as sodium acetate used or produced as a by-product in the production process (mainly alkali metal hydroxide and polyacetic acid used as a saponification catalyst). Derived from a reaction product with acetic acid produced by saponification of vinyl), organic acid such as acetic acid (organic acid occluded in PVA at the time of reaction with diketene when introducing acetoacetate group into PVA resin, etc. ), Organic solvents such as methanol and methyl acetate (derived from a reaction solvent for PVA resin, a cleaning solvent for producing AA-PVA, etc.) may partially remain.

[Glyoxylate (B)]
The glyoxylate (B) used in the present invention will be described.
Examples of the glyoxylate (B) include metal salts and amine salts of glyoxylic acid. Examples of the metal salt include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel and copper, and other zinc And metal salts of glyoxylic acid such as aluminum, and amine salts include salts of amines such as ammonia, monomethylamine, dimethylamine, and trimethylamine and glyoxylic acid.
Among these, a metal salt is preferable in that a cured layer having excellent water resistance is obtained, and an alkali metal salt is particularly preferable in terms of excellent workability of the coating liquid.

  As a method for producing glyoxylate (B), a known method can be used. For example, (1) a method based on a neutralization reaction of glyoxylic acid, (2) an acid whose glyoxylic acid and acid dissociation constant are larger than glyoxylic acid. And (3) a method by alkaline hydrolysis of glyoxylic acid ester (see, for example, JP-A No. 2003-300926). In particular, when the alkaline compound used for the neutralization reaction with glyoxylic acid is highly water-soluble, the method (1) is preferably used, and the resulting glyoxylate (B) has low water-solubility and has an acid dissociation constant of glyoxyl. When the water salt of the acid salt larger than the acid is high, the method (2) is preferably used.

The method (1) is usually carried out using water as a medium, glyoxylic acid and an alkaline compound, for example, various metal hydroxides or amine compounds are reacted in water, and the precipitated glyoxylate is filtered off. It can be produced by drying.
The method (2) is also generally carried out in water, and glyoxylate can be obtained in the same manner as the method (1). Examples of the acid salt having a larger dissociation constant than glyoxylic acid used in the method (2) include, for example, alkali metal or alkaline earth metal salts of aliphatic carboxylic acids such as sodium acetate, calcium acetate, and calcium propionate. Can be mentioned.

  Note that the resin composition of the present invention may contain raw materials used in the production of glyoxylate, impurities contained in the raw materials, by-products during production, etc., for example, glyoxylic acid, metal hydroxide Products, amine compounds, aliphatic carboxylates, glyoxal, oxalic acid, oxalate, glycolic acid or glycolate may be contained.

  The glyoxylate (B) in the present invention has an aldehyde group acetalized with an alcohol having 3 or less carbon atoms such as methanol or ethanol, a diol having 3 or less carbon atoms such as ethylene glycol or propylene glycol, and the like. And hemiacetalized compounds. Such an acetal group and a hemiacetal group have reactivity with various base materials in the same manner as the aldehyde group because the alcohol is easily eliminated in water or at a high temperature and takes an equilibrium state with the aldehyde group.

  The content of glyoxylate (B) is usually 0.1 to 30% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 100 parts by weight of AA-PVA-based resin (A). 15% by weight, more preferably 4 to 10% by weight. If the content is too small, the water resistance of the cured layer tends to be insufficient, and conversely if too large, the stability of the coating liquid for forming the cured layer tends to decrease.

  In addition, in this invention, although glyoxylate (B) is used as a crosslinking agent of AA-ized PVA-type resin (A), within the range which does not inhibit the effect of this invention, AA-type PVA-type resin (A) is used. You may use together a well-known thing as a crosslinking agent. Such cross-linking agents include water-soluble titanium compounds and polyvalent metal compounds such as water-soluble zirconium, amine compounds such as ethylenediamine and metaxylylenediamine, hydrazine compounds such as adipic acid dihydrazide, and methylol groups such as methylolated melamine. Examples thereof include compounds and aldehyde group-containing compounds such as glyoxal.

[Fluorine-containing nonionic surfactant (C)]
The fluorine-containing nonionic surfactant (C) used in the present invention will be described.
The fluorine-containing nonionic surfactant (C) used in the present invention may be any nonionic surfactant containing at least one fluorine atom in its structure.

  The number of fluorine atoms contained in the fluorine-containing nonionic surfactant (C) is usually 1 to 100, preferably 3 to 50, particularly preferably 5 to 30. If the number of fluorine atoms is too large, the antifogging property tends to decrease.

The structural site containing a fluorine atom in the fluorine-containing nonionic surfactant (C) is preferably a fluoroalkyl group, particularly preferably a perfluoroalkyl group.
The number of carbon atoms contained in the fluoroalkyl group or perfluoroalkyl group is usually 1 to 50, preferably 2 to 30, particularly preferably 4 to 25, and more preferably 6 to 20. When there are too many carbon numbers, there exists a tendency for anti-fogging property to fall.

The nonionic structure site in the fluorine-containing nonionic surfactant (C) may be a hydrophilic site such as a hydroxyl group, an amino group, an ester structure, an amide structure, an ether structure,
An ether structure is preferable, an oxyalkylene structure is particularly preferable, and an oxyethylene structure is more preferable.
Such an oxyethylene structure may have a repeating unit, and the number of such repeating is usually 5 to 100, preferably 10 to 80, particularly preferably 15 to 50. If the number of repeating units is too small, the anti-fogging property tends to decrease, and if too large, the workability tends to decrease.

The weight molecular weight of the fluorine-containing nonionic surfactant (C) is usually 100 to 10,000, preferably 200 to 7,000, particularly preferably 300 to 5,000.
If the weight molecular weight is too small, the antifogging property tends not to be sustained, and if it is too large, it tends to be difficult to mix with the resin.

The HLB of the fluorine-containing nonionic surfactant (C) is usually 6 or more, preferably 8 or more, and particularly preferably 10 or more.
If the HLB is too low, the solubility in water tends to decrease, and the dispersibility in the coating liquid tends to drop. In addition, the upper limit of HLB is 20 normally.

  The HLB (Hydrophilie-Lipophile Balance) is an HLB value according to Davies' theory, and is a value represented by HLB = Σ (the number of hydrophilic groups) + Σ (the number of lipophilic groups) +7.

Specific examples of the fluorine-containing nonionic surfactant (C) include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and the like. Fluorine substitution products of polyoxyethylene structure-containing ether compounds, polyoxyethylene structure-containing ester compounds such as polyethylene glycol dilaurate, polyethylene glycol distearate, etc., and trade names include Florard (Sumitomo 3M ( Product name), Surflon (Asahi Glass Co., Ltd. product name), Unidyne (Daikin Kogyo Co., Ltd. product name), MegaFuck (Dainippon Ink Co., Ltd. product name), F-Top (Tochem Products) Ltd.) trade name), and the like.
Among these, perfluoroalkyloxyethylene oxide is preferable in terms of workability due to high water solubility and transparency of the film, and α-perfluorononenyloxy-ω-methylpolyethylene oxide is particularly preferable.

Content of a fluorine-containing nonionic surfactant (C) is 0.001-20 weight part normally with respect to 100 weight part of AA-ized PVA-type resin (A), Preferably 0.01-5 weight% Particularly preferably, it is 0.05 to 3% by weight, more preferably 0.1 to 1% by weight.
When the content is too small, the antifogging property and the antibacterial adhesion property tend to decrease, and when the content is too large, the transparency of the resin composition tends to decrease.

  Thus, a resin composition containing the components (A) to (C) of the present invention is obtained.

  In this invention, it is preferable to use as a film which bridge | crosslinks this resin composition to make a cured layer, and contains this cured layer and a support body.

〔the film〕
The film is a cured layer obtained by crosslinking the resin composition of the present invention, specifically, a cross-linked product of glyoxylate (B) of AA-PVA-based resin (A) and a fluorine-containing nonionic surfactant ( The cured layer containing C) preferably has a layer structure directly laminated on the support.
Such a cured layer is formed by applying a coating liquid comprising a resin composition containing an AA-PVA-based resin (A), glyoxylate (B), and a fluorine-containing nonionic surfactant (C) to a support, and then drying. Formed.

Examples of the material for the support include, for example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyolefins such as polyethylene and polypropylene, and polyamide, polycarbonate, polystyrene, polyvinyl chloride, acrylic resin, and the like. Can do.
Among these, polyesters excellent in strength, durability, dimensional stability, and transparency are preferable, and polyethylene terephthalate is particularly preferable.

Such polyethylene terephthalate (hereinafter abbreviated as PET) is mainly composed of ethylene glycol and terephthalic acid, but other dicarboxylic acid components and glycol components as long as the object of the present invention is not impaired. May be copolymerized.
Examples of the dicarboxylic acid component include isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and cyclohexane-1,4-dicarboxylic acid. Examples of the glycol component include propylene glycol, butanediol, neopentyl glycol, diethylene glycol and the like.

As the support, any of an unstretched film, a uniaxially stretched film, and a biaxially stretched film can be used, but a biaxially stretched film is preferable from the viewpoint of transparency and strength.
Moreover, the thickness of this support body is 1-500 micrometers normally, Preferably it is 3-250 micrometers, Most preferably, it is 5-200 micrometers.
If the thickness of the support is too thin, the strength when the antifogging film or antibacterial film is obtained tends to be insufficient, and if it is too thick, the flexibility tends to be impaired.

  The above support, particularly PET film, usually contains various additives such as inorganic fine particles, waxes, antioxidants, antistatic agents, crystal nucleating agents, thickeners, heat stabilizers, anti-coloring agents. An agent, an ultraviolet absorber, and the like may be contained.

  Moreover, it is also preferable to use a plasma-treated film as the support, and it is particularly preferable in terms of adhesiveness to the cured layer that plasma treatment is performed on the surface laminated with the cured layer.

In such plasma treatment, a high-frequency voltage is applied between the opposing electrodes to discharge, the atmosphere gas is brought into a plasma state, and the surface of the object to be treated is exposed to the plasma state gas to activate the surface. .
As such an atmospheric gas, nitrogen, oxygen, argon, helium, or the like can be used. Among them, nitrogen is preferably used in terms of safety, exhaust gas aftertreatment, running cost, and the like.

Processing the intensity of the plasma treatment is usually 0.1~100W / cm ^2, particularly 0.2~80W / cm ^2, in particular the range of 0.5 to 50 / cm ² is preferably used. When the treatment strength is too weak, the surface treatment effect of the support is small, and there is a tendency that sufficient adhesion with the cured layer cannot be obtained. Further, if the treatment strength is too strong, the surface of the support may be deteriorated.

  The flow rate of the atmospheric gas during the plasma processing is usually 1 to 5000 L / min per 1 m of the effective width of the plasma processing surface, and particularly in the range of 2 to 2500 L / min. If the flow rate is too small, the amount of plasma generated may be small and a sufficient treatment effect may not be obtained. If the flow rate is too high, the amount of gas used increases, which is disadvantageous in terms of cost.

Furthermore, in addition to the plasma treatment, a surface treatment for irradiating energy rays such as ultraviolet rays, electron beams, and ion rays can be used in combination. In particular, UV sources include D2 lamps, high pressure mercury lamps, low pressure mercury lamps, Xe lamps, Hg-Xe lamps, halogen lamps, arc discharges, corona discharges, silent discharge discharge lamps, excimer lasers, Ar + lasers, Kr + lasers. A laser oscillation device such as an N2 laser is preferably used.
The surface treatment with such energy rays can be performed before, after or simultaneously with the plasma treatment.

As said coating liquid, it is preferable to set it as the aqueous coating liquid containing (A)-(C) component, and it is a good solvent of AA-ized PVA-type resin especially, and water from the point with a small environmental load. It is preferable that it is the aqueous coating liquid which uses as a main medium.
In addition, for the purpose of adjusting the drying speed and adjusting the wettability with the support, an organic solvent having miscibility with water, for example, alcohols having 1 to 3 carbon atoms such as methanol and ethanol, acetone and methyl ethyl ketone, etc. It is also possible to add a small amount of these ketones.
In addition, such aqueous coating liquids include additives such as inorganic fine particles, ultraviolet absorbers, antioxidants, antifoaming agents, antifungal agents, antiseptics, leveling agents, etc. within the range not impairing the characteristics of the present invention. May be blended.

  The concentration of the aqueous coating solution is usually 1 to 30% by weight, preferably 3 to 20% by weight, and particularly preferably 5 to 15% by weight. If the concentration is too small, the thickness of the coating layer obtained by one application and drying becomes small, so that a plurality of coatings may be required to obtain a desired thickness. On the other hand, if the concentration is too large, the viscosity of the coating solution increases, and the workability during coating may decrease, or it may be difficult to obtain a coating layer having a uniform thickness.

The pH of such an aqueous coating solution is usually from 2 to 10, preferably from 3 to 10, particularly preferably from 4 to 9, and the adjustment thereof can be carried out with inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, citric acid, tartaric acid. It can carry out by addition of organic acids, such as. If the pH is too low, it may cause corrosion of the equipment used for the production of the coating liquid or the coating on the support. Therefore, countermeasures are necessary. The properties tend to decrease, the viscosity tends to increase, and the pot life tends to be shortened.

In addition, the method for preparing such an aqueous coating solution is not particularly limited.
(I) A method of mixing an AA-PVA-based resin, glyoxylate, and fluorine-containing nonionic surfactant, separately dissolved in advance,
(Ii) A method in which a glyoxylate and a fluorine-containing nonionic surfactant are added to and mixed with an aqueous solution of an AA-PVA-based resin,
(Iii) AA-PVA-based resin and fluorine-containing nonionic surfactant, which are separately dissolved in advance, and a glyoxylate salt,
(Iv) AA-PVA-based resin and glyoxylate, which are separately dissolved in advance, and a fluorine-containing nonionic surfactant,
Etc.

In coating the aqueous coating solution thus obtained on the above-mentioned support (the surface on which the plasma treatment has been applied in the case of plasma treatment), the roll coater method, the air doctor method, the blade coater method, A known coating method such as can be used.
Since the coating amount varies depending on the concentration of the coating solution, it cannot be generally specified, but is usually 1 to 10000 g / m ² , preferably 10 to 5000 g / m ² , particularly preferably 100 to 2000 g / m ² . A range of ² is preferably used.

The coating layer coated on the support is then dried. However, the drying method is not particularly limited, and a known method can be used. The heat source can be hot air, infrared rays, radiant heat, or those. A combination of these can be used.
As drying temperature, it is 70-150 degreeC normally, Preferably it is 80-130 degreeC, Most preferably, it is 90-120 degreeC. Further, the drying time varies depending on the drying temperature and cannot be generally described, but is usually 1 to 20 minutes, preferably 3 to 10 minutes.
Industrially, it is desirable that the coating step and the drying step of the above-described coating liquid be performed continuously.

  The thickness of the cured layer in the film of the present invention is usually 1 to 1000 μm, preferably 2 to 400 μm, particularly preferably 3 to 100 μm, and particularly preferably 5 to 20 μm. The strength of the hardened layer may be insufficient, and there is a tendency that antifogging properties and antibacterial adhesion properties are not sufficiently exhibited. If it is too thick, warping may occur due to a difference in dimensional change in the thickness direction due to moisture absorption etc. There is.

In addition to the cured layer containing the cross-linked product of the AA-PVA-based resin by glyoxylate salt and the fluorine-containing nonionic surfactant (C), the film of the present invention thus obtained has a further function. Other layers can be stacked.
For example, by providing a pressure-sensitive adhesive layer on the surface opposite to the surface on which the hardened layer of the support is laminated, it is possible to facilitate attachment to the glass surface.
Moreover, durability can be improved by providing a protective layer having moisture permeability on the cured layer.

  The total thickness of the film of the present invention is usually 2 to 2000 μm, preferably 5 to 1000 μm, and particularly preferably 10 to 100 μm. If the thickness is too thin, the strength may be insufficient or the handleability may be difficult when sticking to glass or the like. Conversely, if it is too thick, the flexibility tends to be insufficient and the handleability tends to decrease. There is.

  The film of the present invention thus obtained can be usefully used as an antifogging film, an antibacterial film, an agricultural film and the like. Moreover, the coating agent formed by containing the resin composition containing the components (A) to (C) of the present invention can be usefully used as a coating solution for metal surface treatment.

Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to the examples as long as the gist thereof is not exceeded.
In the examples, “parts” and “%” mean weight basis.

[Production Example 1: AA-PVA-based resin (1)]
In a ribbon blender with temperature controller, unmodified PVA resin (average polymerization degree 1200, saponification degree 99.2 mol%) is charged into a kneader, 3600 parts, and 1000 parts of acetic acid is added to swell, and stirred at a rotation speed of 20 rpm. Then, after the temperature was raised to 60 ° C., 550 parts of diketene was added dropwise over 3 hours, and the reaction was further continued for 1 hour. After completion of the reaction, the mixture was washed with methanol and dried at 70 ° C. for 6 hours to obtain AA-PVA resin (1).
The obtained AA-modified PVA resin (1) had an AA degree of 5.3 mol%, a saponification degree of 98.9 mol%, and an average degree of polymerization of 1200.

[Production Example 2: Sodium Glyoxylate]
To 456 g (3.10 mol) of 50% glyoxylic acid aqueous solution in a 2 L two-necked reactor, 645 g (3.22 mol) of 20% aqueous sodium hydroxide solution was added, and the resulting white crystals were filtered and washed with water. Drying at 1 ° C. for 1 hour gave 210 g (1.84 mol, yield 59.5%) of sodium glyoxylate.

The following were used as the fluorine-containing nonionic surfactant (C).
.Alpha.-perfluorononenyloxy-.omega.-methylpolyethylene oxide (manufactured by Neos, trade name "Furgent 215M": ethylene oxide chain average number of repetitions 15)
Α-perfluorononenyloxy-ω-methyl polyethylene oxide (manufactured by Neos, trade name “Fargent 250”: average number of ethylene oxide chain repeats 22)

<Example 1>
One surface of a PET film (“Lumirror T60” manufactured by Toray Industries, Inc., 100 μm thick) was subjected to plasma treatment under the conditions shown below.
Equipment: “Atmospheric pressure plasma surface treatment equipment” manufactured by Sekisui Chemical Co., Ltd.
Processing intensity: 28 W / cm ²
Conveyance speed: 1000mm / s
Nitrogen flow rate: 25 mL / min

Next, 100 parts of a 10% aqueous solution of AA-PVA resin (1) obtained in Production Example 1 is added to 0.5 part of sodium glyoxylate obtained in Production Example 2 (100 parts of AA-PVA resin). 5 parts), 0.1 part of TF 215M was added and mixed and stirred to obtain an aqueous coating solution.
Such a coating solution is coated on the surface of the PET film subjected to plasma treatment with a 100 μm applicator and dried in a hot air dryer at 105 ° C. for 5 minutes to obtain a film having a cured layer having a thickness of 10 μm. It was.

<Example 2>
In Example 1, a film was obtained in the same manner as in Example 1 except that the fluorine-containing nonionic surfactant (C) was changed from the solvent 215M to the solvent 250.

<Comparative Example 1>
In Example 1, a film was obtained in the same manner as in Example 1 except that no footage 215M was added.

<Comparative example 2>
A film was obtained in the same manner as in Example 1 except that sodium glyoxylate was not blended in Example 1.

  The films obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated for water contact angle, antifogging property, and antimicrobial adhesion in the following manner. The results are shown in Table 1.

<Water contact angle>
The resulting film was conditioned for 1 week in an atmosphere of 23 ° C. × 50% RH, and then the water contact angle was measured using a contact angle meter (FAMAS) manufactured by Kyowa Interface Science in the same atmosphere.

<Anti-fogging property>
A 200 ml beaker (manufactured by Asahi Glass Co., Ltd., “PYREX (registered trademark) IWAKI TE-32”, height 9 cm) is charged with 60 ° C. hot water up to a height of 4 cm from the bottom, and is obtained at the mouth of the bottle. The film was placed so that the cured layer was on the inside, and the time until fogging with steam was measured.
(Evaluation)
○… Not cloudy even after 1 hour △… Over 10 minutes and clouded within 1 hour ×… Clouded within 10 minutes

<Adherence to bacteria>
On the cured layer of the film, S. aureus solution with a bacterial concentration of 1.0 × 10 ⁵ cfu / ml, S. aureus solution with 1.0 × 10 ⁷ cfu / ml (prepared with PBS (phosphate buffered saline)) After holding each at 25 ° C. for 1 hour, it was washed 10 times with PBS, and the bacteria adhered to the gold-deposited coating surface were observed with the Hitachi Electron Microscope System “TM1000” for image analysis measurement. The number of bacteria was counted using a soft WinRoof.
Moreover, the same test was done using the PET film which has not applied the said coating liquid as an unprocessed film used as a reference, and the antimicrobial adhesion was evaluated as follows. The PBS used was obtained by dissolving 160 g of NaCl, 4 g of KCl, 58 g of Na ₂ HPO ₄ and ₄ g of KH ₂ PO ₄ in 2034 g of pure water. The pH of this solution is 7.3.
(Evaluation)
○: The number of bacteria attached is 0
Δ: The number of attached bacteria is 0 or more and less than 5 ×: The number of attached bacteria is 5 or more

From the above results, the film having a cured layer obtained from the resin composition containing the AA-PVA-based resin, the glyoxylate salt, and the fluorosurfactant of Examples 1 and 2 exhibits excellent antifogging properties. It can be seen that the bacteria are difficult to adhere.
This is because the water contact angle is small, so that the water attached to the film tends to spread out and is difficult to keep in a state where water droplets are attached, so that the film is less likely to become cloudy, and bacteria attached to the film are attached. It is difficult to wash off easily, so that the bacteria on the film are difficult to propagate.

  On the other hand, it was found that the film of Comparative Example 1 containing no fluorine-containing nonionic surfactant was inferior in both antifogging property and antibacterial adhesion, and that of Comparative Example 2 containing no glyoxylate. It can be seen that the film is excellent in anti-fogging property, but inferior in antimicrobial adhesion.

The film of the present invention is excellent in anti-fogging property, and can be imparted with anti-fogging property by sticking to glass, plastic, etc. Since it is difficult to cause various infectious diseases due to bacteria adhering to the film and propagating, it can be applied to window glass of buildings, mirrors in bathrooms and bathrooms, food showcases, various displays, and the like.
Furthermore, it is also useful for coating agents containing the resin composition containing the components (A) to (C) of the present invention, and it is possible to make the substrate surface hydrophilic by coating it on a substrate such as metal. In addition, since the adherence of bacteria is low, even if it is used for a long time, it is difficult to cause various infectious diseases due to bacteria adhering to the film and propagating. Applicable.

Claims (10)

  A resin composition comprising an acetoacetyl group-containing polyvinyl alcohol resin (A), a glyoxylate (B), and a fluorine-containing nonionic surfactant (C).   The resin composition according to claim 1, wherein the glyoxylate (B) is an alkali metal salt of glyoxylic acid.   The content of glyoxylate (B) is 0.1 to 30 parts by weight with respect to 100 parts by weight of the acetoacetyl group-containing polyvinyl alcohol resin (A). Resin composition.   The resin composition according to any one of claims 1 to 3, wherein the fluorine-containing nonionic surfactant (C) contains a perfluoroalkyl group and an oxyalkylene structure.   The content of the fluorine-containing nonionic surfactant (C) is 0.001 to 20 parts by weight with respect to 100 parts by weight of the acetoacetyl group-containing polyvinyl alcohol resin (A). The resin composition in any one of -4.   A film comprising a support and a cured layer obtained by crosslinking the resin composition according to claim 1.   The film according to claim 6, wherein the cured layer has a thickness of 1 to 1000 μm.   An anti-fogging film characterized in that the film according to claim 6 or 7 is used for an anti-fogging application.   An antibacterial film, wherein the film according to claim 6 or 7 is used for antibacterial applications.   A coating agent comprising the resin composition according to claim 1.